Liquid composition with fungicide, bactericidal and bacteriostatic activity

ABSTRACT

The invention concerns a phytosanitary fungicide, bactericidal or bacteriostatic composition comprising at least a mineral salt, a copper oxide or hydroxide suspended in an aqueous emulsion of at least a terpene derivative.

This application is a 371 application of PCT/FR99/02036, filed Aug. 24,1999.

The subject of the present invention is a liquid composition withfungicidal, bacteriostatic or bactericidal activity, and methods for thepreparation and use of the composition.

It has long been known to use phytopharmaceutical products based oninorganic salts, oxides or hydroxides of copper, in particular for theirfungicidal properties (vine downy mildew and the like) but also fortheir bactericidal power (bacterial canker of peach and apricot trees,bacteriosis of apple and pear trees caused by pseudomonas, and the like)or their bacteriostatic power which prevents bacterial diseases frombecoming established.

The fungicidal and bactericidal activity of copper depends on the natureof the copper compound and on the quality of its manufacture.

The “Bordeaux mixture” has been used for over a century for thetreatment of grape vine. First prepared by the viticulturist, and thenmanufactured industrially, it is obtained by accurately neutralizing asolution of copper sulfate with a milk of lime. This mixture, brought toneutrality (pH=7) is then dried, ground and micronized.

Among the other products based on copper, there may be mentioned copperoxichloride, copper hydroxide, copper carbonate, copper(I) oxide, andthe like.

These inorganic salts, oxides or hydroxides of copper, used alone or incombination with other compounds, are generally provided in the form ofwettable powders, dispersible granules, suspension concentrates,dustable powders, and the like.

The inorganic salts, oxides or hydroxides of copper may also be combinedwith inorganic fungicides, in particular sulfur, or organic fungicidesto form, in the latter case, organocopper compounds.

Among the organic active substances, there may be mentioned inparticular folpel, maneb, mancozeb, propineb, zineb, cymoxanil,metiram-zinc.

The formulations are provided in the forms described above.

With the exception of the dustable powders, the other compositionsgenerally comprise surfactants, wetting agents, dispersing agents,emulsifiers, antifoams and the like, which contribute to the stabilityof the formulations and then to the use of the products, and inparticular to their dispersion in water for the production of mixturesfor treatment.

In addition to the choice of inorganic salts, oxides or hydroxides ofcopper and to the selection of surfactants, formulators seek to enhancethe efficacy of the products because the degree of protection from acopper compound against attacks by fungi and bacteria is closely relatedto its capacity to saturate the surface of the plant by forming amicroscopic film of particles. Adherence to the plant followed byresistance to strong rain is also one of the objectives sought by themanufacturers.

For some time now, and in particular for the treatment of grape vine,many products using copper hydroxide as active substance have beenappearing on the market.

The optimization of the formulations based on copper hydroxide, inparticular of the suspension concentrates, has been carried out by:

-   -   the search for a specific structure for the particles:        crystallized fine needles, acicular structure;    -   the improvement in the reduction of their size obtained by        micronization or by a chemical method for manufacture of copper        hydroxide, it being possible for said size to reach from 0.3 to        0.4 μm;    -   the choice of the surfactants and co-formulants capable of        stabilizing the formulation and of increasing the efficacy        thereof.

FR 2 599 592 describes liquid formulations for the preventive andcurative treatment of cryptogamic diseases of the oidium type comprisinga lipophilic inorganic active substance consisting of fine ground ormicronized sulfur, in suspension in a liquid composed of a mixture ofpine oil and water, the pine oil enhancing the efficacy of the sulfur.

The work by the inventors which has led to the present invention hasmade it possible to establish that the efficacy of inorganic salts,oxides or hydroxides of copper can, surprisingly, be enhanced when thesewere combined with a terpenic derivative.

This discovery is unexpected insofar as persons skilled in the art didnot expect the efficacy of inorganic salts, oxides or hydroxides ofcopper to be enhanced by the addition of terpenic derivatives because ofthe difference in physicochemical nature between the inorganic salts,oxides or hydroxides of copper, on the one hand, and the sulfur metalspecies, on the other hand, in particular because of the fact thatsulfur is essentially lipophilic, while the inorganic salts, oxides orhydroxides of copper are essentially hydrophilic.

The subject of the invention is a fungicidal, bactericidal orbacteriostatic plant-protection composition comprising at least oneinorganic salt, one oxide or one hydroxide of copper in suspension in anaqueous emulsion of at least one terpenic derivative.

The aqueous emulsions also cover the microemulsions.

The inorganic salt, oxide or hydroxide of copper consists of one or of amixture of those mentioned above, copper hydroxide (Cu(OH)₂) beingpreferred.

The terpenic derivatives for the purposes of the present invention areorganic molecules containing ten carbon atoms in their structure.

They are therefore essentially monoterpenes.

The terpenic derivatives may be acyclic, monocyclic or bicyclic.

The following examples may be mentioned in particular:

1) the terpenic hydrocarbons:

a) acyclic terpenic hydrocarbons: myrcene, alloocimene, and the like;

b) monocyclic terpenic hydrocarbons: dipentene, terpinolene, p-cymene,limonene, and the like;

c) bicyclic terpenic hydrocarbons: α-pinene, β-pinene or δ-3-carene, andthe like;

2) the following compounds:

a- the oxidized derivatives; cineols;

b- the terpenic alcohols: borneol, fenchol, menthanol, terpineols,geraniol, 1-terpinen-4-ol, and the like;

c- the aldehydes and ketones: camphor, fenchone;

3) the mixtures of the products cited above;

4) the essential oils containing the above mixtures in variousproportions, for example Malalenca alternifolia essential oil (ortea-tree oil);

5) the pine oils of natural or synthetic origin which are defined asbeing mixtures of terpenic hydrocarbons and alcohols.

Pine oil containing 90% of terpenic alcohols is most particularlypreferred.

The suspension according to the invention advantageously also containsat least one surfactant for its emulsifying, wetting, crystal growthinhibiting properties, and the like.

It is possible to use an anionic, cationic, amphoteric, zwitterionicand/or nonionic surfactant.

The anionic and nonionic surfactants, alone or in the form of a mixture,are preferred.

The following compounds are particularly well suited to the aim of theinvention:

-   -   ethoxylated fatty acids,    -   ethoxylated fatty alcohols,    -   calcium alkylbenzenesulfonate,    -   alkylnaphthalenesulfonates,    -   ethoxylated alkylphenols,    -   EO/PO block copolymers,    -   PO/EO block copolymers,    -   diisopropylnaphthalenesulfonates,    -   dimethylnaphthalenesulfonates,    -   di-n-butylnaphthalenesulfonates,    -   ethoxylated dodecylphenols,    -   sodium dodecylbenzenesulfonate,    -   phosphoric esters of alkyl polyethers (acid forms and/or salts),    -   phosphoric esters of ethoxylated arylphenols (acid forms and/or        salts),    -   phosphoric esters of ethoxylated polyarylphenols (acid forms        and/or salts),    -   ethoxylated castor oil,    -   isopropylnaphthalenesulfonates,    -   lignosulfonates,    -   methyldinapthalenesulfonates,    -   methylnaphthalenesulfonates,    -   n-butylnapthalenesulfonates,    -   ethoxylated octylphenols,    -   phenyl sulfonates,    -   polyalkylnaphtylmethanesulfonates,    -   polyacrylates,    -   ethoxylated polyarylphenols,    -   polycarboxylates,    -   polyvinylpyrrolidone and derivatives thereof,    -   salts of sulfonated cresol-formalin condensates,    -   salts of condensates of naphthalenesulfonic acid,    -   salts of acrylic acid-acrylic ester copolymers,    -   salts of maleic acid-olefin copolymers,    -   salts of maleic anhydride-isobutylene copolymers,    -   ethoxylated alkylphenol sulfates,    -   ethoxylated polyarylphenol sulfates,    -   sulfosuccinates,    -   taurates,    -   ethoxylated tristyrylphenols . . .

The suspension concentrates of the present invention advantageouslycomprise from 200 to 600 g/l, preferably 300 to 500 g/l of copper, ofthe inorganic salt, oxide or hydroxide of copper expressed relative tothe copper element. The contents of terpenes in the formulations arebetween 50 and 400 g/l, preferably 80 to 200 g/l.

The contents of surfactant(s) in the formulations are between 20 and 100g/l, preferably 30 to 60 g/l.

The liquid compositions of the invention, also called suspensionconcentrates or “flowable concentrates” may be prepared by micronizingthe active substance, optionally mixed with a portion or all of theother ingredients, by passing through a specific mill (for example aball mill of the ®DYNO-MILL type) until a stable homogeneous suspensionis obtained.

Mechanical micronization may be avoided and a simple mixing may besufficient if an active substance which is already micronized eithermechanically or by the method of synthesis, is used. In either case, themicronization is performed until a diameter of the particles ofinorganic salts, oxides or hydroxides of copper not greater than 6 μm isobtained.

An example of copper hydroxide which may be suitable for the preparationof a composition by simple mixing is the technical copper hydroxidemanufactured by NORDEUTSCHE AFFINERIE, marketed by URANIA AGROCHEM GmbH.

It is also possible to use a copper hydroxide prepared in accordancewith the methods described in U.S. Pat. No. 3,194,749 and U.S. Pat. No.4,944,935.

The compositions of the invention have a markedly improved fungicidal,bactericidal or bacteriostatic activity compared with the compositionsof the state of the art not containing a terpenic derivative.

This gain in efficacy makes it possible to reduce the quantities ofcopper applied to the plants during treatments.

This dose reduction is very advantageous because it makes it possible toreduce the sometimes depressive action which copper exerts on plants andits phytotoxicity toward some plants.

The subject of the invention is also the use of a terpenic derivativefor enhancing the efficacy of an inorganic salt, an oxide or a hydroxideof copper in a plant-protection, in particular fungicidal, bactericidalor bacteriostatic, composition.

The subject of the invention is, furthermore, a method of treatingplants with a product based on an inorganic salt, oxide or hydroxide ofcopper, characterized in that an effective quantity of plant-protectionmixture prepared by mixing, in aqueous form, a composition of aninorganic salt, oxide or hydroxide of copper in suspension in an aqueousemulsion containing at least one terpenic derivative, is sprayed on theplant to be treated.

Examples of compositions based on an inorganic salt, oxide or hydroxideof copper and a terpene according to the invention as well as theresults obtained with these compositions on vine downy mildew(Plasmopara viticola) will be given below.

EXAMPLES 1 TO 3 OF COMPOSITIONS ACCORDING TO THE INVENTION

Formula A Formula B Formula C Content of copper: from 300 to 310 g/lCopper hydroxide 36.76% 501 g/l 36.76% 500 g/l 36.76% 500 g/l Pine oil(containing 90% of terpenic alcohols) 6.60% 90 g/l 9.78% 133 g/l 12.94%176 g/l Urea 4.00% 54.5 g/l 4.00% 54.4 g/l 4.00% 54.4 g/l TENSIOFIX ®BCZ (sulfated alcohol) 1.00% 13.6 g/l 1.00% 13.6 g/l 1.00% 13.6 g/lTENSIOFIX ® LX (lignosulfonate) 1.00% 13.6 g/l 1.00% 13.6 g/l 1.00% 13.6g/l TENSIOFIX ® D40 (cationic/nonionic surfactant) 1.00% 13.6 g/l 1.00%13.6 g/l 1.00% 13.6 g/l Silcone-containing antifoam 0.05% 0.7 g/l 0.05%0.7 g/l 0.05% 0.7 g/l BARAGEL ® 24 1.50% 20.5 g/l 1.00% 13.6 g/l 0.50%6.8 g/l Water 48.09% 656.1 g/l 45.41% 617.5 g/l 42.75% 581.4 g/l

Active substance: Technical copper hydroxide (content of copper: 62.05%)

Composition prepared by mixing the various ingredients and thenmicronizing by passing through a mill of the ®DYNO-MILL type.

TENSIOFIX®: OMNICHEM trademark

BARAGEL®: NL-CHEMICAL trademark.

EXAMPLE 4 Example of Composition According to the Invention

Formula D Content of copper: 396.1 g/l Copper hydroxide 43.55% 659 g/lPine oil (containing 90% of terpenic alcohols) 8.62% 130.5 g/lPolyarylphenol phosphate which is ethoxylated 1.67% 25.3 g/l andneutralized with triethanolamide Aqueous solution containing 35% of asodium 4.91% 74.3 g/l salt of a sulfonated cresol-formalin condensateMonoethylene glycol 5.84% 88.4 g/l Heteropolysaccharide of the xanthangum type 0.11% 1.7 g/l Silicone-containing antifoam qs qs Water qs 100qs 100

Active substance: Technical copper hydroxide (content of copper=62.4%)marketed by URANIA AGROCHEM GmbH

-   -   Particle Size        -   <13 μm: 100%        -   <6.6 μm: 92.4%        -   <4.7 μm: 81.5%        -   <3.3 μm: 64.8%        -   <2.4 μm: 47.6%

Composition prepared by simple mixing of the various ingredients.

EXAMPLE 5 Example of Composition According to the Invention

Formula E Content of copper: 407 g/l Copper hydroxide 45.00%  619.2 g/l Pine oil (containing 90% of terpenic alcohols) 7.80% 119.8 g/l Polyarylphenol phosphate which is ethoxylated 2.20% 33.8 g/l andneutralized with triethanolamine Aqueous solution containing 35% of asodium 5.00% 76.8 g/l salt of a sulfonated cresol-formalin condensateGlycerol 1.40% 21.5 g/l Urea 6.00% 92.2 g/l Silicone-containing antifoamqs qs Heteropolysaccharide of the xanthan gum type  0.125%  1.9 g/lWater qs 100 qs 100

Active substance: Technical copper hydroxide (content of copper=62.88%)

Composition prepared by mixing the various ingredients and thenmicronizing by passing through a ball mill of the ®DYNO-MILL type.

EXAMPLE 6 Results of Experimentation on Vine Downy Mildew (Plasmoparaviticola)

1st Trial: Scores on Leaves

Dose/ha of Doses/ha % of damage on leaves Product Copper Pine oil 1stscore 2nd score NTC / / / 68.75% 97.50% Formula B 5 l 1500 g 665 g43.75% 83.75% Formula C 5 l 1500 g 880 g 40.63% 84.38% Formula A 7.5 12250 g 675 g 43.13% 85.63% Formula B 7.5 l 2250 g 998 g 29.38% 70.63%Formula C 7.5 l 2250 g 1320 g  26.25% 68.13% SC formulation 8.8 l 3000 g/ 38.13% 82.50% (state of the art) WP formulation 6 kg 3000 g / 42.50%78.13% (state of the art)

Study on young plants

Grape vine, Cabernet-Sauvignon cultiver

Trials under misting with artificial contaminations

NTC: Non treated control SC: Suspension concentrate

WP: Wettable powder

2nd Trial: Scores on Bunches of Grapes

Dose/ha Doses/ha of Pine 1st score 2nd score Product Copper oilIntensity Frequency Intensity Frequency NTC / / / 72.85% 14.29% 98.20%58.56% Formula D   5 l 2050 g 650 g 6.41% 0.33% 27.50% 2.29% SCformulation 6.7 l 2030 g / 9.09% 0.75% 36.03% 2.82% (state of the art)

Study on fruit-bearing plants

Grape vine, Cabernet-Sauvignon cultiver

Trials under misting with artificial contaminations

NTC: Non treated control SC: Suspension concentrate

3rd Trial: Scores on Leaves

Dose/ha Doses/ha % of of Pine damage on % of Product Copper oil leavesdefoliating Formula D   5 l 2050 g 650 g 22.50% 48.75% SC formulation6.7 l 2030 g / 36.25% 60.00% (state of the art)

Study on fruit-bearing plants

Grape vine, Cabernet-Sauvignon cultiver

Trials under misting with artificial contaminations

SC: Suspension concentrate

4th Trial: Scores on Leaves

Dose/ha of Doses/ha 1st score 2nd score 3rd score Product Copper Pineoil Intensity Frequency Intensity Frequency Intensity Frequency NTC / // 15.0%  64.5%  62.83%  99.0% 58.65%  84.0% Formula E 4  1 1630 g 480 g1.8% 6.8% 1.63% 16.0% 1.47% 14.3% Formula E 5  1 2040 g 600 g 1.5% 6.8%0.90%  9.0% 1.33% 15.0% Formula E 6.25  1   2540 g 750 g 2.2% 8.5% 1.22%11.5% 1.16% 11.0% SC formulation 7  1 2520 g / 2.0% 8.8% 2.20% 19.0%1.91% 15.3% (state of the art)

Study on fruit-plants

Grape vine, Grenache

Trials under misting with atificial contaminations

NTC: Non treated control SC: Suspension concentrate

5th Trial: Scores on Bunches of Grapes

Dose/ha of Doses/ha 1st score 2nd score Product Copper Pine oilIntensity Frequency Intensity Frequency NTC / / / 9.90%  57.5%  67.70% 99.8% Formula E 4  1 1630 g 480 g 0.20% 2.3% 7.05% 42.8% Formula E 5  12040 g 600 g 0.15% 2.6% 7.30% 36.3% Formula E 6.25  1   2540 g 750 g0.01% 0.5% 1.70% 14.8% SC formulation 7  1 2520 g / 9.09% 1.5% 4.10%29.5% (state of the art)

Study on fruit-bearing plants

Grape vine, Grenache

Trials under misting with artificial contaminations

NTC: Non treated control SC: Suspension concentrate

6th Trial: Scores on Leaves

Dose/ha of Doses/ha 1st score 2nd score 3rd score Product Copper Pineoil Intensity Frequency Intensity Frequency Intensity Frequency NTC / // 24.3%  84.5%  27.83%  97.8%  27.34%  91.8%  Formula E 4  1 1630 g 480g 0.6% 3.5% 0.90% 4.5% 0.35% 2.3% Formula E 5  1 2040 g 600 g 0.2% 2.3%0.23% 2.3% 0.17% 1.3% SC formulation 7  1 2520 g / 0.2% 2.0% 0.45% 2.0%0.18% 2.0% (state of the art)

Study on fruit-bearing plants

Grape vine, Grenache

Trials under misting with artificial contaminations

NTC: Non treated control SC: Suspension concentrate

17th Trial: Scores on Bunches of Grapes

Dose/ha of Doses/ha Produce Copper Pine oil Intensity Frequency NTC / // 6.5% 39.8% Formula E 4 l 1630 g 480 g 0.1% 0.8% Formula E 5 l 2040 g600 g 0.1% 0.4% Formula E 6.25 l   2540 g 750 g 0.0% 0.4% SC formulation7 l 2520 g / 0.1% 0.9% (state of the art)

Study on fruit-bearing plants

Grape vine, Grenache

Trials under misting with artificial contaminations

NTC: Non treated control SC: Suspension conentrate

1. A fungicidal, bactericidal or bacteriostic plant-protectioncomposition comprising at least one inorganic salt, one oxide or onehydroxide of copper in suspension in an aqueous emulsion of at least onemonoterpene.
 2. The composition of claim 1, wherein said inorganic salt,oxide or hydroxide of copper is selected from the group consisting ofcopper hydroxide, copper oxychloride, copper carbonate, copper(I) oxideand mixtures thereof.
 3. The composition of claim 1, wherein saidinorganic salt, oxide or hydroxide of copper is copper hydroxide.
 4. Thecomposition of claim 1, wherein copper is present from 200 to 600 g/l,in the form of an inorganic salt, oxide or hydroxide of copper.
 5. Thecomposition of claim 1, wherein the diameter of the particles of saidinorganic salt, oxide or hydroxide of copper is not greater than 6 μm.6. The composition of claim 1, wherein said monoterpene is selected fromthe group consisting of terpenic hydrocarbons, oxidized derivatives ofterpenic hydrocarbons, terpenic alcohols, terpenic aldehydes and ketonesand mixtures thereof.
 7. The composition of claim 1, wherein saidmonoterpene is a mixture of terpenic hydrocarbons and terpenic alcohols.8. The composition of claim 1, wherein said monoterpene is an essentialoil.
 9. The composition of claim 1, wherein said monotermene is a pineoil.
 10. The composition of claim 1, wherein said monoteroene is a pineoil containing 90% by weight of terpenic alcohols.
 11. The compositionof claim 1, wherein said at least one monoterpene is (are) present from50 to 400 g/l.
 12. The composition of claim 1, further comprising atleast one surfactant.
 13. The composition of claim 1, further comprisingfrom 20 to 100 g/l of surfactant(s).
 14. The composition of claim 1,further comprising a surfactant selected from the group consisting of:ethoxylated fatty acids, ethoxylated fatty alcohols, calciumalkylbenzenesulfonate, alkylnaphthalenesulfonates, ethoxylatedalkylphenols, EO/PO block copolymers, PO/EO block copolymers,diisopropyinaphthalenesulfonates, dimethylnaphthalenesulfonates,di-n-butylnaphthalenesulfonates, ethoxylated dodecylphenols, sodiumdodecylbenzenesulfonate, phosphoric esters of alkyl polyethers (acidforms and/or salts), phosphoric esters of ethoxylated arylphenols (acidforms and/or salts), phosphoric esters of ethoxylated polyarylphenols(acid forms and/or salts), ethoxylated castor oil,isopropylnaphthalenesulfonates, lignosulfonates,methyldinapthalenesulfonates, methylnaphthalenesulfonates,n-butylnapthalenesulfonates, ethoxylated octylphenols, phenylsulfonates, polyalkylnaphtylmethanesulfonates, polyacrylates,ethoxylated polyarylphenols, polyvinylpyrrolidone and derivativesthereof, salts of sulfonated cresol-formalin condensates, salts ofcondensates of naphthalenesulfonic acid, salts of acrylic acid-acrylicester copolymers, salts of maleic acid-olefin copolymers, salts ofmaleic anhydride-isobutylene copolymers, ethoxylated alkylphenolsulfates, ethoxylated polyarylphenol sulfates, sulfosuccinates,taurates, and ethoxylated tristyrylphenols.
 15. A method of preparing afungicidal, bactericidal or bacteriostic plant-protection compositioncomprising at least one inorganic salt, one oxide or one hydroxide ofcopper in suspension in an aqueous emulsion of at least one monoterpene,comprising micronizing said inorganic salt, oxide or hydroxide of copperand other ingredients of the composition comprising at least onemonoterpene, water and at least one surfactant until a stablehomogeneous suspension is obtained in which the size of the particles isless than 6 μm.
 16. A method of preparing a fungicidal, bactericidal orbacteriostic plant-protection composition comprising at least oneinorganic salt, one oxide or one hydroxide of copper in suspension in anaqueous emulsion of at least one terpenic derivative, comprisingadmixing said inorganic salt, oxide or hydroxide of copper, having adiameter not greater than 6 μm, with other ingredients of thecomposition comprising at least one terpenic derivative, water and atleast one surfactant until a stable homogeneous suspension is obtained.17. A method of enhancing the efficacy of an inorganic salt, oxide orhydroxide of copper in a plant-protection composition, comprisingcombining said inorganic salt, oxide or hydroxide of copper insuspension in an aqueous emulsion with at least one monoterpene.
 18. Amethod of treating plants with a product based on an inorganic salt,oxide or hydroxide of copper, comprising spraying an effective quantityof a plant-protection mixture prepared by mixing, in aqueous form, acomposition of an inorganic salt, oxide or hydroxide of copper insuspension in an aqueous emulsion containing at least one monoterpene,on the plant to be treated.